The present invention relates to a polyethylene resin composition excellent in moldability and capable of providing moldings having excellent pliability.
The present invention relates to a soft resin composition containing a polyethylene resin, which is capable of providing moldings excellent, particularly, in pliability and heat resistance and has an excellent moldability.
The present invention also relates to an ethylene/xcex1-olefin copolymer composition suitable for use mainly in packaging films. More particularly, the present invention relates to an ethylene/xcex1-olefin copolymer composition which is, as compared with the conventional ethylene copolymer compositions, excellent in film-moldability and capable of high-speed molding, and also capable of providing a film excellent in machanical strength properties, low temperature heat-sealing properties and heat-sealing stability, and further in slip characteristics and anti-blocking properties thereby being excellent in suitability for high-speed filling upon packaging by automaticcally filling, and to a film from the same.
Polyethylene resins include various kinds of resins, such as high-pressure low-density polyethylene resins, high-density polyethylene resins and linear low-density polyethylene resins including ethylene/xcex1-olefin copolymers.
Of these, the low-density polyethylene resins are excellent in the balance between pliability and heat resistance and, therefore, are widely used for gaskets of injection molding machines, and for various packing, tube and sheet materials.
The conventional low-density polyethylene resins are excellent in heat resistance but do not have sufficient pliability. Therefore, improvement in the properties has been desired.
For example, a method of blending various elastomers (e.g., ethylene/propylene copolymer rubber and ethylene/1-butene copolymer rubber) with the low-density polyethylene resin to give pliability to the resins has been proposed.
However, such a method has a drawback in that, when the conventional ethylene elastomer is blended with the low-density polyethylene resins, the pliability of the resins is improved but the heat resistance thereof becomes remarkably worse.
Accordingly, now desired is development of the polyethylene resin composition capable of providing moldings being well-balanced in pliability and heat resistance, and exhibiting an improved flowability in various molding processes.
Among the polyethylene resins as mentioned above, for example, the high-pressure low-density polyethylene resins, the high-density polyethylene resins and the linear low-density polyethylene resins including ethylene/xcex1-olefin copolymers have been molded into films and widely used in various fields, such as in packaging of products from the past.
Specifically, the films of the linear low-density polyethylene resins including ethylene/xcex1-olefin copolymers are used for sealants of various packaging materials, because the linear low-density polyethylene resins as film materials can be made at low energy consumption (i.e., small production cost) of production, as compared with the conventional high-pressure low-density polyethylenes, and are excellent in heat-sealability through contaminants, hot tack and mechanical properties, such as tear strength and impact strength.
Though the suitability for high-speed filling upon packaging by automatic filling machines is required for the purpose of packaging, the film made singly from the linear low-density ethylene/xcex1-olefin copolymer does not always sufficiently satisfy the required handling characteristics and suitability for high-speed filling.
Accordingly, now desired is development of the resins capable of providing films having more excellent low temperature heat-sealing properties, sealing stability, slip characteristics and antiblocking properties.
The linear low-density ethylene/xcex1-olefin copolymer is low in melt tension for its molecular weight, as compared with the high-pressure polyethylene. Therefore, it has a drawback in that, when they are molded into films at high speed in inflation molding, rocking or breakage of bubbles is liable to occur. The linear low-density ethylene/xcex1-olefin copolymer has a further drawback in that, since the number of branchings in its molecular chain is small, the flowability thereof in high-shear region becomes worse.
Accordingly, in order to solve the above problems, many kinds of compositions or films have been proposed. For example, there have been proposed a composition made by blending a low-crystalline ethylene copolymer having a density of not more than 0.905 g/cm3 with the ethylene/xcex1-olefin copolymer (Japanese Patent L-O-P No. 34145/1982) and a composition made by blending an ethylene/vinyl acetate copolymer with the ethylene/xcex1-olefin copolymer (Japanese Patent L-O-P No. 109543/1984).
However, films of these compositions could not solve the above problems and, therefore, there is room for improvement in melt tension, flowability in high shearing region, low temperature heat-sealing properties, mechanical properties including tear strength, transparency, and antiblocking properties.
The present invention has been made in order to solve the above problems associated with the prior art.
An object of the invention is to provide a resin composition excellent in moldability and capable of providing moldings having excellent pliability.
Another object of the invention is to provide particularly a soft resin composition containing a polyethylene resin, which is capable of providing moldings excellent in pliability and heat resistance and has an excellent moldability.
Still another object of the present invention is to provide an ethylene/xcex1-olefin copolymer, resin composition and a film therefrom, which composition is excellent in heat stability and stability for high-speed molding, and can provide films excellent in low temperature heat-sealing properties and sealing stability, and, further, in slip characteristics and anti-blocking properties thereby being excellent in handling properties and suitability for high-speed filling upon packaging by automatically filling.
The resin composition of the present invention is a composition comprising:
a polyethylene resin (A) at an amount of 100 parts by weight; and
a long-chain branched ethylene/xcex1-olefin random copolymer (B) comprising ethylene and an xcex1-olefin having 3 to 20 carbon atoms at an amount of 0.5 to 5000 parts by weight (that is, the composition contains 2 to 20000 parts by weight of the polyethylene resin (A) based on 100 parts by weight of the copolymer (B)),
wherein the polyethylene resin (A) has:
(a) a melt flow rate (MFR) (ASTM D 1238, 190xc2x0 C., a load of 2.16 kg) of 0.01 to 150 g/10 min and;
(b) a density of 0.901 to 0.970 g/cm3, and
wherein the ethylene/xcex1-olefin random copolymer (B) has:
(a) a density of not more than 0.900 g/cm3;
(b) an intrinsic viscosity (xcex7), as measured in decalin at 135xc2x0 C., of 0.3 to 3.0 dl/g;
(c) a glass transition temperature (Tg) of not more than xe2x88x9250xc2x0 C.;
(d) a crystallinity, as measured by X-ray diffractometry, of less than 40%;
(e) a molecular weight distribution (Mw/Mn), as measured by GPC, of not more than 3.0;
(f) a B value, as determined by the 13C-NMR spectrum and the following equation, of 1.0 to 1.4; and
(g) a ratio gxcex7* of the intrinsic viscosity (xcex7) determined in the property (b) to the intrinsic viscosity (xcex7)blank of a linear ethylene-propylene copolymer having the same weight-average molecular weight (measured by a light scattering method) as the copolymer rubber (B) and having an ethylene content of 70% by mol, (xcex7)/(xcex7)blank, of 0.2 to 0.95,
xe2x80x83B value=(POE)/(2xc2x7(PE)xc2x7(PO)
wherein (PE) and (PO) are respectively a molar fraction of the units derived from ethylene and a molar fraction of the units derived from the xcex1-olefin in the copolymer rubber (B), and (POE) is a proportion of the number of the ethylene/xcex1-olefin sequences to the number of all the dyad sequences.
B value=(POE)/(2xc2x7(PE)xc2x7(PO)
wherein (PE) and (PO) are respectively a molar fraction of the units derived from ethylene and a molar fraction of the units derived from the xcex1-olefin in the copolymer rubber (B), and (POE) is a proportion of the number of the ethylene/xcex1-olefin sequences to the number of all the dyad sequences.
The soft resin composition of the present invention is a composition comprising:
a polyethylene resin (A-X) at an amount of 100 parts by weight; and
a long-chain branched ethylene/xcex1-olefin random copolymer (B-Y) comprising ethylene and an xcex1-olefin having 3 to 20 carbon atoms at an amount of 50 to 5000 parts by weight (that is, the composition contains 2 to 200 parts by weight of the polyethylene resin (A-X) based on 100 parts by weight of the copolymer (B-Y)),
wherein the polyethylene resin (A-X) has:
(a) a melt flow rate (MFR) (ASTM D 1238, 190xc2x0 C., a load of 2.16 kg) of 3 to 150 g/10 min; and
(b) a density of 0.901 to 0.970 g/cm3, and
wherein the ethylene/xcex1-olefin random copolymer (B-Y) has:
(a) a density of not more than 0.900 g/cm3;
(b) an intrinsic viscosity (xcex7), as measured in decalin at 135xc2x0 C., of 0.3 to 3.0 dl/g;
(c) a glass transition temperature (Tg) of not more than xe2x88x9250xc2x0 C.;
(d) a crystallinity, as measured by X-ray diffractometry, of less than 40%;
(e) a molecular weight distribution (Mw/Mn), as measured by GPC, of not more than 3.0;
(f) a B value, as determined by the 13C-NMR spectrum and the above equation, of 1.0 to 1.4; and
(g) a ratio gxcex7* of the intrinsic viscosity (xcex7) determined in the property (b) to the intrinsic viscosity (xcex7)blank of a linear ethylene-propylene copolymer having the same weight-average molecular weight (measured by a light scattering method) as the copolymer rubber (B) and having an ethylene content of 70% by mol, (xcex7)/(xcex7)blank, of 0.2 to 0.95.
The ethylene/xcex1-olefin copolymer resin composition of the present invention is a composition comprising:
a polyethylene resin (A-xcex1) in an amount of 100 parts by weight; and
a long-chain branched ethylene/xcex1-olefin random copolymer (B-xcex1) in an amount of 5 to 67 parts by weight (that is, the composition contains 60 to 95 parts by weight of the polyethylene resin (A-xcex1) and the remainings of the copolymer (B-xcex1), based on 100 parts by weight of the total amount of the polyethylene resin (A-xcex1) and the copolymer (B-xcex1),
wherein the polyethylene resin (A-xcex1) is a linear ethylene/xcex1-olefin copolymer (A-0) comprising ethylene and xcex1-olefin having 4 to 20 carbon atoms and has:
(a) a density of 0.901 to 0.940 g/cm3; and
(b) a melt flow rate (MFR) of 0.01 to 20 g/10 min, and
wherein the long-chain branched ethylene/xcex1-olefin random copolymer (B-xcex1) has:
(a) a density of 0.860 to 0.900 g/cm3;
(b) a melt flow rate (MFR) of 0.01 to 20 g/10 min;
(c) an intrinsic viscosity (xcex7), as measured in decalin at 135xc2x0 C., of 0.3 to 3.0 dl/g;
(d) a glass transition temperature (Tg) of not more than xe2x88x9250xc2x0 C.;
(e) a crystallinity, as measured by X-ray diffractometry, of less than 40%;
(f) a molecular weight distribution (Mw/Mn), as measured by GPC, of not more than 3.0;
(g) a B value, as determined by the 13C-NMR spectrum and the above equation, of 1.0 to 1.4; and
(h) a ratio gxcex7* of the intrinsic viscosity (xcex7) determined in the property (c) to the intrinsic viscosity (xcex7)blank of a linear ethylene-propylene copolymer having the same weight-average molecular weight (measured by a light scattering method) as the copolymer rubber (B-xcex1) and having an ethylene content of 70% by mol, (xcex7)/(xcex7)blank, of 0.2 to 0.95.
Each of the ethylene/xcex1-olefin random copolymers used in the above compositions is preferably an ethylene/xcex1-olefin random copolymer prepared by randomly copolymerizing ethylene and an xcex1-olefin having 3 to 20 carbon atoms in the presence of a metallocene catalyst comprising a metallocene compound represented by the following formula (I): 
wherein M is a transition metal atom of Group IVB of the periodic table,
R1 is a hydrocarbon group having 1 to 6 carbon atoms;
R2, R4, R5 and R6 may be identical with or different from each other and are each hydrogen, a halogen atom or a hydrocarbon group of 1 to 6 carbon atoms,
R3 is an aryl group of 6 to 16 carbon atoms which may be substituted with a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms or an organic silyl group,
X1 and X2 are each independently hydrogen, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and
Y is a divalent hydrocarbon group of 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group of 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94NR7xe2x80x94, xe2x80x94P(R7) xe2x80x94, xe2x80x94P(O) (R7)xe2x80x94, xe2x80x94BR7xe2x80x94 or xe2x80x94AlR7xe2x80x94 (in the formulae, the R7 is hydrogen or a halogen atom, or a hydrocarbon group of 1 to 20 carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbon atoms).
The film (ethylene/xcex1-olefin copolymer resin film) of the invention is preferably made from the above resin composition (ethylene/xcex1-olefin copolymer composition).
In the present invention, the film is preferably produced by inflation molding.
The resin compositions and the use thereof according to the invention are described in detail hereinafter.
The resin composition (including the soft resin composition and ethylene/xcex1-olefin resin composition, and so forth) of the present invention comprises a polyethylene resin (A) and a long-chain branched ethylene/xcex1-olefin random copolymer (B) in the specific ratio.
Hereinafter, the soft resin composition is mainly described at first and, next, the ethylene/xcex1-olefin copolymer resin composition is described.
The polyethylene resin (A) used in the invention may be a homopolymer of ethylene or a random copolymer of ethylene and xcex1-olefin, preferably of ethylene and xcex1-olefin having 4 to 20 carbon atoms. Further, the polyethylene resin (A) may be linear or branched.
Examples of the xcex1-olefin having 4-20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl -1-decene, 11-methyl-1-dodecene and 12-ethyl-1-tetradecene. These olefins are used singly or in combination of two or more kinds.
The polyethylene resin (A) used in the invention has MFR (melt flow rate: ASTM D 1238, 190xc2x0 C., a load of 2.16 kg) of 0.01 to 150 g/min. Particularly, when MFR is 3 to 150 g/10 min, preferably 5 to 100 g/10 min, more preferably 7 to 50 g/10 min, the resultant resin composition is excellent in melt-flowability, namely excellent in moldability, and capable of providing moldings having an improved balance between pliability and heat resistance.
The polyethylene resin (A) desirably has a density of not more than 0.970 g/cm3, preferably 0.901 to 0.970 g/cm3, especially 0.901 to 0.930 g/cm3. The polyethylene resin (A) having such density gives the soft resin composition excellent in moldability and having an improved balance between pliability and heat resistance.
In the soft resin composition of the invention, the ethylene/xcex1-olefin random copolymer (B) described below is contained at an amount of 0.5 to 5000 parts by weight based on 100 parts by weight of the polyethylene resin (A). The resin composition described above is excellent in moldability and capable of providing moldings having excellent pliability. Particularly, when the (soft) resin composition contains the ethylene/xcex1-olefin random copolymer (B) in an amount of 67 to 2000 parts by weight, more preferably 83 to 1000 parts by weight, especially 100 to 500 parts by weight, based on 100 parts by weight of the polyethylene resin (A), moldings having an excellent balance between pliability and heat resistance can be provided and the soft resin compositions excellent in moldability can be obtained.
In other words, particuarly, in case of the soft resin composition of the present invention, the polyethylene resin (A) is desirably contained in an amount of 2 to 200 parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, especially 20 to 100 parts by weight, based on 100 parts by weight of the ethylene/xcex1-olefin random copolymer (B).
The polyethylene resins (A) as described above can be obtained by a conventional process.
The ethylene/xcex1-olefin copolymer as described above can be obtained by, for example, copolymerizing ethylene and xcex1-olefin having 4 to 20 carbon atoms in the presence of a transition metal catalyst.
For example, the density of the linear ethylene/xcex1-olefin copolymer can be controlled with the kind and copolymerized amount of the xcex1-olefin used, and the melt flow rate can be controlled with the kind and amount of a chain transfer agent.
The catalysts and the polymerization process for producing the polymers are not particularly limited. As the catalysts, employable are Ziegler-Natta catalyst, Phillips catalyst, a metallocene catalyst and so on. Ziegler-Natta catalyst includes a compound of a transition metal of Group IV of the periodic table, such as Ti-type and Zr-type, and an olefin polymerization catalyst comprising a compound of a transition metal of Group V of the periodic table (V-type) and an organoaluminum compound. As the polymerization process, employable are a slurry polymerization, gas phase polymerization, solution polymerization and so on.
The ethylene/xcex1-olefin random copolymer (B) used in the invention is a long-chain branched ethylene/xcex1-olefin random copolymer of ethylene and xcex1-olefin having 3 to 20 carbon atoms.
Examples of the xcex1-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene and 12-ethyl-1-tetradecene. These olefins are used singly or in combination of two or more kinds.
The ethylene/xcex1-olefin random copolymer (B) has a density of not more than 0.900 g/cm3, preferably not more than 0.895 g/cm3, more preferably not more than 0.890 g/cm3.
The ethylene/xcex1-olefin random copolymer (B) has an intrinsic viscosity (xcex7), as measured in decalin at 135xc2x0 C., of 0.3 to 3.0 dl/g, preferably 0.5 to 2.0 dl/g. The ethylene/xcex1-olefin random copolymer (B) having the intrinsic viscosity in the above range has excellent blending properties with the polyethylene resin (A). Moreover, use of the ethylene/xcex1-olefin random copolymer (B) having an intrinsic viscosity within the above range provides the soft resin composition containing polyethylene resin, which has high flowability and excellent moldability.
The ethylene/xcex1-olefin random copolymer (B) has a glass transition temperature (Tg), as measured by DSC (differential scanning calorimeter), of not more than xe2x88x9250xc2x0 C.
The ethylene/xcex1-olefin random copolymer (B) has a crystallinity, as measured by X-ray diffractometry, of less than 40%, preferably not more than 30%. Use of the ethylene/xcex1-olefin random copolymer (B) having a crystallinity of less than 40% provides the soft resin composition containing polyethylene resin which is excellent in pliability.
The ethylene/xcex1-olefin random copolymer (B) desirably has a molecular weight distribution (Mw/Mn), as measured by GPC, of not more than 3.0 and a parameter (B value), as determined by the 13C-NMR spectrum, which indicates a randomness in sequences of polymerized comonomers, of 1.0-1.4.
This B value of the ethylene/xcex1-olefin random copolymer (B) is an index of distribution of constituent units derived from each comonomer in a chain made by copolymerization, and it can be determined based on the following equation.
B value=(POE)/(2xc2x7(PO)xc2x7(PE))
wherein (PE) and (PO) are respectively a molar fraction of the units derived from ethylene and a molar fraction of the units derived from the xcex1-olefin in the ethylene/xcex1-olefin random copolymer rubber, and
(POE) is a proportion of the number of the xcex1-olefin/ethylene sequences to the number of all the dyad sequences in the copolymer rubber (B).
Concretely, the PE, PO and POE values are obtained as follows.
In a tube having a diameter of 10 mmxcfx86, about 200 mg of ethylene/xcex1-olefin random copolymer is homogeneously dissolved in 1 ml of hexachlorobutadiene to prepare a sample. 13C-NMR spectrum of the sample is measured under the following conditions.
(Measuring Conditions)
Measuring temperature: 120xc2x0 C.
Measuring frequency: 20.05 MHz
Spectrum width: 1500 Hz
Filter width: 1500 Hz
Pulse repetition time: 4.2 sec
Pulse width: 7 xcexcsec
Number of integration times: 2000 to 5000
The PE, PO and POE values are obtained from the 13C-NMR spectrum thus measured in accordance with the proposals of G. J. Ray (Macromolecules, 10,773 (1977)), J. C. Randall (Macromolecules, 15,353 (1982)) and K. Kimura (Polymer, 25,441 (1984))
In this connection, the B value obtained from the above equation becomes 2 when both monomers are mutually distributed in the ethylene/xcex1-olefin copolymer resin. The B value becomes 0 when the polymer is a perfect block copolymer in which both monomers are completely separated.
Use of the ethylene/xcex1-olefin random copolymer (B) having B value within the above range provides the soft resin composition containing polyethylene resin, which has excellent heat resistance.
The ethylene/xcex1-olefin random copolymer (B) has a gxcex7* value of 0.2 to 0.95, preferably 0.4 to 0.9, more preferably 0.5 to 0.85.
The gxcex7* value is defined by the following equation.
gxcex7*=(xcex7)/(xcex7)blank
wherein (xcex7) is an intrinsic viscosity measured in the property (c), and (xcex7)blank is an intrinsic viscosity of a linear ethylene/propylene copolymer which has the same weight-average molecular weight (measured by a light scattering method) as the ethylene/xcex1-olefin random copolymer and has an ethylene content of 70% by mol.
The fact that the gxcex7* value of the ethylene/xcex1-olefin random copolymer is not more than 0.95 indicates the formation of a long-chain branching in the molecule.
The long-chain branched ethylene/xcex1-olefin random copolymer (B) having the above-described properties can be obtained by randomly copolymerizing ethylene and xcex1-olefin having 3 to 20 carbon atoms in the presence of a metallocene catalyst containing a specific metallocene compound.
The metallocene catalyst used in the process is not particularly limited so long as it contains a metallocene compound (A). For example, the metallocene catalyst may comprises a metallocene compound (A) in addition to an organoaluminum-oxy compound (B) and/or a compound reacting with the metallocene compound (A) to form an ion pair (C) (sometimes simply referred to xe2x80x9ccompound (C)xe2x80x9d hereinafter). The metallocene catalyst may be comprises an organoaluminum compound (D) in addition to the metallocene compound (A), and the organoaluminum-oxy compound (B) and/or the compound (C).
The metallocene compound [A] employable for preparing the long-chain branched ethylene/xcex1-olefin random copolymer (B) that is used in the invention is, for example, a compound represented by the following formula [I]. 
In the formula [I], M is a transition metal atom of Group IVB of the periodic table, specifically titanium, zirconium or hafnium, particularly preferably zirconium.
Substituent R1 
R1 is a hydrocarbon group of 1 to 6 carbon atoms, and examples thereof include alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl and cyclohexyl; and alkenyl groups, such as vinyl and propenyl.
Of these, preferable are alkyl groups whose carbon bonded to the indenyl group is primary carbon. More preferable are alkyl groups of 1 to 4 carbon atoms, and particularly preferred are methyl and ethyl.
Substituents R2, R4, R5 and R6 
R2, R4, R5 and R6 may be the same as or different from each other, and are each hydrogen, a halogen atom or the same hydrocarbon group of 1 to 6 carbon atoms as described for R1.
The halogen atom is fluorine, chlorine, bromine or iodine.
Substituent R3 
R3 is an aryl group of 6 to 16 carbon atoms. This aryl group may be substituted with a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms or an organosilyl group.
Examples of the aryl groups include phenyl, xcex1-naphthyl, xcex2-naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl and biphenylyl. Of these, phenyl, naphthyl, anthracenyl and phenanthryl are preferable.
Examples of the hydrocarbon groups of 1 to 20 carbon atoms serving as substituents of the aryl groups include:
alkyl groups, such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl and adamantyl;
alkenyl groups, such as vinyl, propenyl and cyclohexenyl;
arylalkyl groups, such as benzyl, phenylethyl and phenylpropyl; and
aryls groups, such as the above-exemplified aryl groups, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, methylnaphthyl and benzylphenyl.
Examples of the organosilyl groups include trimethylsilyl, triethylsilyl and triphenylsilyl.
Substituents X1 and X2 
X1 and X2 are each hydrogen, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms which may be substituted with halogen, an oxygen-containing group or a sulfur-containing group. Examples of the halogen atoms and the hydrocarbon groups are the same as those mentioned above.
Examples of the oxygen-containing groups include hydroxyl group; alkoxy groups, such as methoxy, ethoxy, propoxy and butoxy; aryloxy groups, such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; and arylalkoxy groups, such as phenylmethoxy and phenylethoxy.
Examples of the sulfur-containing groups include substituents wherein oxygen is replaced with sulfur in the above-exemplified oxygen-containing groups; sulfonato groups, such as methylsulfonato, trifluoromethanesulfonato, phenylsulfonato, benzylsulfonato, p-toluenesulfonato, trimethylbenzenesulfonato, triisobutylbenzenesulfonato, p-chlorobenzenesulfonato and pentafluorobenzenesulfonato; and sulfinato groups, such as methylsulfinato, phenylsulfinato, benzylsulfinato, p-toluenesulfinato, trimethylbenzenesulfinato and pentafluorobenzenesulfinato.
Of these, X1 and X2 are each preferably a halogen atom or a hydrocarbon group of 1 to 20 carbon atoms.
Y
Y is a divalent hydrocarbon group of 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group of 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalanet tin-containing group, xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94NR7xe2x80x94, xe2x80x94P(R7)xe2x80x94, xe2x80x94P(O)(R7)xe2x80x94, xe2x80x94BR7xe2x80x94 or xe2x80x94AlR7xe2x80x94 (The R7 is hydrogen or a halogen atom, or a hydrocarbon group of 1 to 20 carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbon atoms).
Examples of the divalent hydrocarbon groups of 1 to 20 carbon atoms include alkylene groups, such as methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene;
and arylalkylene groups, such as diphenylmethylene and diphenyl-1,2-ethylene.
Examples of the divalent halogenated hydrocarbon groups include those wherein the above-exemplified divalent hydrocarbon groups of 1 to 20 carbon atoms are halogenated, such as chloromethylene.
Examples of the divalent silicon-containing groups include alkylsilylene, alkylarylsilylene and arylsilylene groups, such as methylsilylene, dimethylsilylene, diethylsilylene, di(n-propyl)silylene, di(i-propyl)silylene, di(cyclohexyl)silylene, methylphenylsilylene, diphenylsilylene, di(p-tolyl)silylene and di(p-chlorophenyl)silylene; and alkyldisilyl, alkylaryldisilyl and aryldisilyl groups, such as tetramethyl-1,2-disilyl and tetraphenyl-1,2-disilyl.
Examples of the divalent germanium-containing groups include those wherein silicon is replaced with germanium in the above-exemplified divalent silicon-containing groups.
R7 is the same halogen atom, hydrocarbon group of 1 to 20 carbon atoms or halogenated hydrocarbon group of 1 to 20 carbon atoms as described above.
Of these, Y is preferably a divalent silicon-containing group or a divalent germanium-containing group, more preferably a divalent silicon-containing group, particularly preferably an alkylsilylene group, an alkylarylsilylene group or an arylsilylene group.
Listed below are examples of the metallocene compounds represented by the above formula [I].
rac-Dimethylsilylene-bis(4-phenyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(1-(2-methyl-4-phenylindenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(xcex1-naphthyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(xcex2-naphthyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(1-anthracenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(2-anthracenyl)-1-indenyl) zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(9-anthracenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(9-phenanthryl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-fluorophenyl)-1-indenyl)zirconium dichioride,
rac-Dimethylsilylene-bis(2-methyl-4-(pentafluorophenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-chlorophenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(m-chlorophenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(o-chlorophenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(o,p-dichlorophenyl)phenyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-bromophenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-tolyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(m-tolyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(o-tolyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(o,oxe2x80x2-dimethylphenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-ethylphenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-i-propylphenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-benzylphenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-biphenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(m-biphenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-trimethylsilylenephenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(m-trimethylsilylenephenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-phenyl-4-phenyl)-1-indenyl)zirconium dichloride,
rac-Diethylsilylene-bis(2-methyl-4-phenyl)-1-indenyl)zirconium dichloride,
rac-Di(i-propyl)silylene-bis(2-methyl-4-phenyl-1-indenyl)}zirconium dichloride,
rac-Di(n-butyl)silyiene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Dicyclohexylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Methylphenylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Diphenylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Di(p-tolyl)silylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichiloride,
rac-Di(p-chlorophenyl)silylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Methylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Ethylene-bis(2-methyl-4-phenyl-1-indenyl) zirconium dichloride,
rac-Dimethylgermylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Dimethylstannylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dibromide,
rac-Dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dimethyl,
rac-Dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium methylchloride,
rac-Dimethylsilyiene-bis(2-methyl-4-phenyl-1-indenyl)zirconium chloride SO2Me,
rac-Dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium chloride OSO2Me,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(xcex1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilyiene-bis{1-(2-ethyl-4-(xcex2-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(2-methyl-1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(5-acenaphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(9-anthracenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(9-phenanthryl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(o-methylphenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(m-methylphenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(p-methylphenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(2,3-dimethylphenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(2,4-dimethylphenyl)indenyl,)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(2,5-dimethylphenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(2,4,6-trimethylphenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(o-chlorophenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(m-chlorophenyl)indenyl)}zirconium dichioride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(p-chlorophenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(2,3-dichlorophenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(2,6-dichlorophenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(3,5-dichlorophenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(2-bromophenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(3-bromophenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(4-bromophenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(4-biphenylyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(4-trimethylsilylphenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-propyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-propyl-4-(xcex1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-propyl-4-(xcex2-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-propyl-4-(2-methyl-1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-propyl-4-(5-acenaphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-propyl-4-(9-anthracenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-propyl-4-(9-phenanthryl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-propyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-propyl-4-(xcex1-naphthyl)indenyl)}zirconium dichioride,
rac-Dimethylsilylene-bis{1-(2-i-propyl-4-(xcex2-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-propyl-4-(8-methyl-9-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylslylene-bis{1-(2-i-propyl-4-(5-acenaphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilyiene-bis{1-(2-i-propyl-4-(9-anthracenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-propyl-4-(9-phenanthryl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-s-butyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-s-butyl-4-(xcex1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilyiene-bis{1-(2-s-butyl-4-(xcex2-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-s-butyl-4-(2-methyl-1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-s-butyl-4-(5-acenaphthyl)indenyl)}zirconium dichioride,
rac-Dimethylsilylene-bis{1-(2-s-butyl-4-(9-anthracenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-s-butyl-4-(9-phenanthryl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-pentyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-pentyl-4-(xcex1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-butyl-4-phenylindenyl)}zirconium dichioride,
rac-Dimethylsilylene-bis{1-(2-n-butyl-4-(xcex1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-butyl-4-(xcex2-naphthyl)indenyl)}zirconium dichioride,
rac-Dimethylsilylene-bis{1-(2-n-butyl-4-(2-methyl-1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-butyl-4-(5-acenaphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-butyl-4-(9-anthracenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-butyl-4-(9-phenanthryl)indenyl)}zirconium dichioride,
rac-Dimethylsilylene-bis{1-(2-i-butyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-butyl-4-(xcex1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-butyl-4-(xcex2-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-butyl-4-(2-methyl-1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-butyl-4-(5-acenaphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-butyl 4-(9-anthracenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-butyl-4-(9-phenanthryl)indenyl)}zirconium dichloride,
rac-Dimethylsilyiene-bis{1-(2-neopentyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-neopentyl-4-(xcex1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-hexyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-hexyl-4-(xcex1-naphthyl)indenyl)}zirconium dichloride,
rac-Methylphenylsilylene-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,
rac-Methylphenylsilyiene-bis{1-(2-ethyl-4-(xcex1-naphthyl)indenyl)}zirconium dichloride,
rac-Methylphenylsilylene-bis{1-(2-ethyl-4-(9-anthracenyl)indenyl)}zirconium dichloride,
rac-Methylphenylsilylene-bis{1-(2-ethyl-4-(9-phenanthryl)indenyl)}zirconium dichloride,
rac-Diphenylsilylene-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,
rac-Diphenylsilylene-bis{1-(2-ethyl-4-(xcex1-naphthyl)indenyl)}zirconium dichioride,
rac-Diphenylsilylene-bis{1-(2-ethyl-4-(9-anthracenyl)indenyl)}zirconium dichloride,
rac-Diphenylsilylene-bis{1-(2-ethyl-4-(9-phenanthryl)indenyl)}zirconium dichloride,
rac-Diphenyisilylene-bis{1-(2-ethyl-4-(4-biphenylyl)indenyl)}zirconium dichiloride,
rac-Methylene-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichioride,
rac-Methylene-bis{1-(2-ethyl-4-(xcex1-naphthyl)indenyl)}zirconium dichloride,
rac-Ethylene-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,
rac-Ethylene-bis{1-(2-ethyl-4-(xcex1-naphthyl) indenyl)}zirconium dichloride,
rac-Ethylene-bis{1-(2-n-propyl-4-(xcex1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylgermyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylgermyl-bis{1-(2-ethyl-4-(xcex1-naphthyl)indenyl)}zirconium dichloride, and
rac-Dimethylgermyl-bis{1-(2-n-propyl-4-phenylindenyl)}zirconium dichloride.
Also employable are compounds wherein zirconium is replaced with titanium or hafnium in the above-exemplified compounds.
In the invention, a racemic modification of the metallocene compound is generally used as the catalyst component, but R type or S type is also employable.
The metallocene compounds mentioned above can be used in combination of two or more kinds.
The metallocene compounds can be prepared in accordance with xe2x80x9cJournal of Organometallic Chem.xe2x80x9d, 288 (1985), pp. 63 to 67 and European Patent Application No. 0,320,762.
Other than the metallocene compound of the formula [I], a compound represented by the following formula [II] is also employable.
LaMX2xe2x80x83xe2x80x83[II]
wherein M is a metal of Group IV of the periodic table or a metal of lanthanide series;
La is a derivative of delocalization xcfx80 bond group and gives restraint geometrical shape to the metal M active site; and
Xs are each independently hydrogen or a halogen atom, or a hydrocarbon group containing 20 or less carbon atoms, silicon or germanium atom, a silyl group or a germyl group.
Of the compounds of the formula [II], preferable are those represented by the following formula [III]. 
In the formula [III], M is titanium, zirconium or hafnium, and X is the same as described above.
Cp is xcfx80-bonded to M and is a substituted cyclopentadienyl group having a substituent Z or its derivative.
Z is oxygen, sulfur, boron or an element of Group IVA of the periodic table.
Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur. Z and Y may together form a condensed ring.
Listed below are examples of the compounds represented by the formula [III].
(Dimethyl(t-butylamide)(tetramethyl-xcex75-cyclopentadienyl)saline)titanium dichloride,
((t-Butylamide)(tetramethyl-xcex75-cyclopentadienyl)-1,2-ethanediyl)titanium dichloride,
(Dibenzyl(t-butylamide)(tetramethyl-xcex75-cyclopentadienyl)silane)titanium dichloride,
(Dimethyl(t-butylamide)(tetramethyl-xcex75-cyclopentadienyl)silane)dibenzyltitanium,
(Dimethyl(t-butylamide)(tetramethyl-xcex75-cyclopentadienyl)silane)dimethyltitanium,
((t-Butylamide)(tetramethyl-xcex75-cyclopentadienyl)-1,2-ethanediyl)dibenzyltitanium,
((Methylamide)(tetramethyl-xcex75-cyclopentadienyl)-1,2-ethanediyl)dineopentyltitanium,
((Phenylphosphide)(tetramethyl-xcex75-cyclopentadienyl)-methylene)diphenyltitanium,
(Dibenzyl(t-butylamide)(tetramethyl-xcex75-cyclopentadienyl)silane)dibenzyltitanium,
(Dimethyl(benzylamide)(xcex75-cyclopentadienyl)silane)di(trimethylsilyl)titanium,
(Dimethyl(phenylphosphide)-(tetramethyl-xcex75-cyclopentadienyl)silane)dibenzyltitanium,
(Tetramethyl-xcex75-cyclopentadienyl)-1,2-ethanediyl)dibenzyltitanium,
(2-xcex75-(Tetramethyl-cyclopentadienyl)-1-methyl-ethanolate(2-))dibenzyltitanium,
(2-xcex75-(Tetramethyl-cyclopentadienyl)-1-methyl-ethanolate(2-))dimethyltitanium,
(2-((4a, 4b, 8a, 9, 9a-xcex7)-9H-Fluorene-9-yl)cyclohexanolate(2-))dimethyltitanium, and
(2-((4a,4b,8a,9,9a-xcex7)-9H-Fluorene-9-yl)cyclohexanolate(2-))dibenzyltitanium.
In the invention, the metallocene compounds represented by the formula [II] can be used in combination of two or more kinds.
Some of titanium compounds are listed above as examples of the metallocene compounds, but compounds wherein titanium is replaced with zirconium or hafnium in the above-exemplified titanium compounds are also employable.
These compounds may be used alone or in combination of two or more kinds.
Of the above-mentioned various metallocene compounds, the metallocene compound represented by the formula [I] is preferably used in the preparation of the long-chained branched ethylene/xcex1-olefin random copolymer.
The organoaluminum oxy-compound [B] used in the invention may be aluminoxane conventionally known or a benzene-insoluble organoaluminum oxy-compound exemplified in Japanese Patent Laid-Open Publication No. 78687/1990.
The conventionally known aluminoxane can be prepared by, for example, the following procedures.
(1) An organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of compounds containing adsorbed water or salts containing water of crystallization, e.g., magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate or cerous chloride hydrate, so as to allow the organoaluminum compound to react with the compound or the salt, followed by recovering aluminoxane as its hydrocarbon solution.
(2) Water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran, followed by recovering aluminoxane as its hydrocarbon solution.
(3) An organotin oxide such as dimethyltin oxide or dibutyltin oxide is allowed to react with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene or toluene.
The aluminooxane may contain a small amount of an organometallic component. Further, it is possible that the solvent or the unreacted organoaluminum compound is distilled off from the recovered solution of aluminoxane and that the remainder is redissolved in a solvent.
Examples of the organoaluminum compounds used for preparing the aluminoxane include:
trialkylaluminums, such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum;
tricycloalkylaluminums, such as tricyclohexylaluminum and tricyclooctylaluminum;
dialkylaluminum halides, such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride;
dialkylaluminum hydrides, such as diethylaluminum hydride and diisobutylaluminum hydride;
dialkylaluminum alkoxides, such as dimethylaluminum methoxide and diethylaluminum ethoxide; and
dialkylaluminum aryloxides, such as diethylaluminum phenoxide.
Of these, particularly preferable are trialkylaluminums and tricycloalkylaluminums.
Also employable as the organoaluminum compound used for preparing the aluminoxane is isoprenylaluminum represented by the formula:
(i-C4H9)xAly(C5H10)z (wherein x, y, z are each a positive number, and zxe2x89xa72x).
The organoaluminum compounds mentioned above can be used in combination of two or more kinds.
Examples of the solvents used for preparing the aluminoxane include:
aromatic hydrocarbons, such as benzene, toluene, xylene, cumene and cymene;
aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane;
alicyclic hydrocarbons, such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane;
petroleum fractions, such as gasoline, kerosine and gas oil; and
halides of these aromatic, aliphatic and alicyclic hydrocarbons, particularly chlorides and bromides thereof.
Also employable are ethers such as ethyl ether and tetrahydrofuran.
Of the solvents, particularly preferable are aromatic hydrocarbons.
The compound which reacts with the metallocene compound [A] to form an ion pair [C] includes Lewis acid, ionic compounds, borane compounds and carborane compounds described in National Publications of international Patent No. 501950/1989 and No. 502036/1989, Japanese Patent Laid-Open Publication No. 179005/1991, No. 179006/1991, No. 207703/1991 and No. 207704/1991, and U.S. Pat. No. 5,321,106.
The Lewis acid includes Mg-containing Lewis acid, Al-containing Lewis acid and B-containing Lewis acid. Of these, B-containing Lewis acid is preferred.
The Lewis acid which contains a boron atom is, for example, a compound represented by the following formula:
BR1R2R3
wherein R1, R2 and R3 are each independently a phenyl group which may have a substituent such as fluorine, methyl or trifluoromethyl, or a fluorine atom.
Examples of the compounds represented by the above formula include trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron and tris(3,5-dimethylphenyl)boron. Of these, particularly preferred is tris(pentafluorophenyl)boron.
The ionic compound employable in the invention is a salt comprising a cationic compound and an anionic compound. The anion reacts with the metallocene compound [A] to render the compound [A] cationic, thereby, to form an ion pair, so that the anion stabilizes the transition metal cation seed. Examples of such anions include organoboron compound anion, organoarsenic compound anion and organoaluminum compound anion. Preferable are anions which are relatively bulky and stabilize the transition metal cation seed. Examples of the cations include metallic cation, organometallic cation, carbonium cation, tripium cation, oxonium cation, sulfonium cation, phosphonium cation and ammonium cation.
More specifically, there can be mentioned triphenylcarbenium cation, tributylammonium cation, N,N-dimethylammonium cation, ferrocenium cation, etc.
In the invention, ionic compounds containing an organoboron compound anion are preferred, and examples thereof include:
trialkyl-substituted ammonium salts, such as triethylammoniumtetra(phenyl)boron, tripropylammoniumtetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammoniumtetra(p-tolyl)boron, trimethylammoniumtetra(o-tolyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammoniumtetra(o-tolyl)boron and tri(n-butyl)ammoniumtetra(4-fluorophenyl)boron;
N,N,-dialkylanilinium salts, such as N,N-dimethylaniliniumtetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron and N,N-2,4,6-pentamethylaniliniumtetra(phenyl)boron;
dialkylammonium salts, such as di(n-propyl)ammoniumtetra(pentafluorophenyl)boron and dicyclohexylammoniumtetra(phenyl)boron; and
triarylphosphonium salts, such as triphenylphosphoniumtetra(phenyl)boron, tri(methylphenyl)phosphoniumtetra(phenyl)boron and tri(dimethylphenyl)phosphoniumtetra(phenyl)boron.
As the ionic compounds containing a boron atom, triphenylcarbeniumtetrakis(pentarluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate and ferroceniumtetra(pentafluorophenyl)borate are also employable in the invention.
Further, the following ionic compounds containing a boron atom are also employable. (In the ionic compounds enumerated below, the counter ion is tri(n-butyl)ammonium, but the counter ion is in no way limited thereto.)
That is, there can be mentioned salts of anion, for example, bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate, bis[tri(n-butyl)ammonium]dodecachlorododecaborate, tri(n-butyl)ammonium-1-carbadecaborate, tri(n-butyl)ammonium-1-carbaundecaborate, tri(n-butyl)ammonium-1-carbadodecaborate, tri(n-butyl)ammonium-1-trimethylsilyl-1-carbadecaborate and tri(n-butyl)ammoniumbromo-1-carbadodecaborate.
Moreover, borane compounds and carborane compounds are also employable. These compounds are used as the Lewis acid or the ionic compounds.
Examples of borane compounds, carborane complex compounds and salts of carborane anions include decaborane(14), 7,8-dicarbaundecaborane(13), 2,7-dicarbaundecaborane(13), undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborane, tri(n-butyl)ammonium-6-carbadecaborate(14), tri(n-butyl)ammonium-6-carbadecaborate(12), tri(n-butyl)ammonium-7-carbaundecaborate(13), tri(n-butyl)ammonium-7,8-dicarbaundecaborate(12), tri(n-butyl)ammonium-2,9-dicarbaundecaborate(12), tri(n-butyl)ammoniumdodecahydride-8-methyl-7,9-dicarbaundecaborate, tri(n-butyl)ammoniumundecahydride-8-ethyl-7,9-dicarbaundecaborate, tri(n-butyl)ammoniumundecahydride-8-butyl-7,9-dicarbaundecaborate, tri(n-butyl)ammoniumundecahydride-8-allyl-7,9-dicarbaundecaborate, tri(n-butyl)ammoniumundecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate and tri(n-butyl)ammoniumundecahydride-4,6-dibromo-7-carbaundecaborate.
Examples of carborane compounds and salts of carboranes include 4-carbanonaborane(14), 1,3-dicarbanonaborane(13), 6,9-dicarbadecaborane(14), dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane and undecahydride-1,3-dimethyl-1,3-dicarbanonaborane.
Furthermore, the following compounds are also employable. (In the ionic compounds enumerated below, the counter ion is tri(n-butyl)ammonium, but the counter ion is in no way limited thereto.)
That is, there can be mentioned salts of metallic carboranes and metallic borane anions, for example, tri(n-butyl)ammoniumbis(nonahydride-1,3-dicarbanonaborate)cobaltate(III), tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)ferrate(III), tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)cobaltate(III), tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)nickelate(III), tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)cuprate(III), tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)aurate(III), tri(n-butyl)ammoniumbis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)ferrate (III), tri(n-butyl)ammoniumbis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)chromate(III), tri(n-butyl)ammoniumbis(tribromooctahydride-7,8-dicarbaundecaborate)cobaltate(III), tri(n-butyl)ammoniumbis(dodecahydridedicarbadodecaborate)-cobaltate(III), bis[tri(n-butyl)ammonium]bis(dodecahydridedodecaborate)-nickelate(III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)chromate(III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)manganate(IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)cobaltate(III) and bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)nickelate(IV).
The compounds [C] mentioned above can be used singly or in combination of two or more kinds.
The organoaluminum compound [D] used in the invention can be represented by, for example, the following general formula (a):
R5nAlX3xe2x88x92nxe2x80x83xe2x80x83(a)
wherein R5 is a hydrocarbon group of 1 to 12 carbon atoms, X is a halogen or hydrogen atom, and n is 1 to 3.
In the formula (a), R5 is a hydrocarbon group of 1 to 12 carbon atoms, e.g., an alkyl group, a cycloalkyl group or an aryl group. Examples of such groups include methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl and tolyl.
Examples of such organoaluminum compounds include:
trialkylaluminums, such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum and tri-2-ethylhexylaluminum;
alkenylaluminums, such as isoprenylaluminum;
dialkylaluminum halides, such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide;
alkylaluminum sesquihalides, such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide;
alkylaluminum dihalides, such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide; and
alkylaluminum hydrides, such as diethylaluminum hydride and diisobutylaluminum hydride.
Also employable as the organoaluminum compound [D] is a compound represented by the following formula (b):
R5nAlY3xe2x88x92nxe2x80x83xe2x80x83(b)
wherein R5 is the same as R5 in the formula (a); Y is xe2x80x94OR6 group, xe2x80x94OSiR73 group, xe2x80x94OAlR82 group, xe2x80x94NR92 group, xe2x80x94SiR103 group or xe2x80x94N(R11)AlR122 group; n is 1 to 2; R6, R7, R8 and R12 are each methyl, ethyl, isopropyl, isobuzyl, cyclohexyl, phenyl or the like; R9 is hydrogen atom, methyl, ethyl, isopropyl, phenyl, trimethylsilyl or the like; and R10 and R11 are each methyl, ethyl or the like.
Examples of such organoaluminum compounds include:
(i) compounds of the formula R5nAl(OR6)3xe2x88x92n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum methoxide;
(ii) compounds of the formula R5nAl(OSiR73)3xe2x88x92n, e.g., (C2H5)2Al(OSi(CH3)3), (iso-C4H9)2Al(OSi(CH3)3) and (iso-C4H9)2Al(OSi (C2H5) 3);
(iii) compounds of the formula R5nAl(OAlR82)3xe2x88x92n, e.g., (C2H5)2Al(OAl(C2H5)2) and (iso-C4H9)2Al(OA1(iso-C4H9)2);
(iv) compounds of the formula R5nAl(NR92)3xe2x88x92n, e.g., (CH3)2Al(N (C2H5)2), (C2H5)2Al(NH (CH3)), (CH3)2Al(NH (C2H5)), (C2H5)2Al[N(Si(CH3)3)2] and (iso-C4H9)2Al[N(Si(CH3)3)2]; and 
(v) compounds of the formula R5nAl(SiR103)3xe2x88x92n, e.g., (iso-C4H9)2Al(Si (CH3)3).
Of these, preferable are organoaluminum compounds of the formulae R53Al , R5nAl(OR6) 3xe2x88x92nand R5nAl(OAlR82)3xe2x88x92n, and particularly preferred are compounds of said formulae wherein R5 is an isoalkyl group and n is 2. The organoaluminum compounds mentioned above can be used in combination of two or more kinds.
The specific metallocene catalyst employable in the invention contains the metallocene compound [A], and the catalyst can be formed from, for example, the metallocene compound [A] and the organoaluminum oxy-compound [B] as mentioned above. The metallocene catalyst may be formed from the metallocene compound [A] and the compound [C], or it may be formed from the metallocene compound [A], the organoaluminum oxy-compound [B] and the compound [C]. In these embodiments, it is particularly preferable to further use the organoaluminum compound [D] in combination.
In the present invention, the metallocene compound [A] is used in an amount of usually about 0.00005 to 0.1 mmol, preferably about 0.0001 to 0.05 mmol, in terms of the transition metal atom, based on 1 liter of the polymerization volume.
The organoaluminum oxy-compound [B] is used in such an amount that the amount of the aluminum atom becomes usually about 1 to 10,000 mol, preferably 10 to 5,000 mol, per 1 mol of the transition metal atom.
The compound which reacts with the metallocene compound [A] to form an ion pair [C] is used in such an amount that the amount of the boron atom becomes usually about 0.5 to 20 mol, preferably 1 to 10 mol, based on 1 mol of the transition metal atom.
The organoaluminum compound [D] is used optionally in an amount of usually about 0 to 1,000 mol, preferably about 0 to 500 mol, based on 1 mol of the aluminum atom in the organoaluminum oxy-compound [B] or the boron atom in the compound [C] which forms an ion pair.
By copolymerizing ethylene and an xcex1-olefin of 3 to 20 carbon atoms using the above-mentioned metallocene catalyst, the long-chain branched ethylene/xcex1-olefin random-copolymer can be obtained with high polymerization activities.
However, even if ethylene and an xcex1-olefin of 3 to 20 carbon atoms are copolymerized using a Group VB transition metal compound catalyst such as a vanadium catalyst, it is impossible to obtain the long-chain branched ethylene/xcex1-olefin random copolymer with high polymerization activity.
In the copolymerization of ethylene and an xcex1-olefin of 3 to 20 carbon atoms, the metallocene compound [A], the organoaluminum oxy-compound [B] and the compound which forms an ion pair [C], and optionally, the organoaluminum compound [D], all of which constitute the metallocene catalyst, may be separately fed to the polymerization reactor, or a preliminarily prepared metallocene catalyst containing the metallocene compound [A] may be added to the polymerization reaction system.
In the preparation of the metallocene catalyst, hydrocarbon solvents which are inert to the catalyst components can be employed.
Examples of the inert hydrocarbon solvents include aliphatic hydrocarbons, such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosine; alicyclic hydrocarbons, such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons, such as benzene, toluene and xylene; and halogenated hydrocarbons, such as ethylene chloride, chlorobenzene and dichloromethane. These hydrocarbon solvents can be used singly or in combination.
The metallocene compound [A], the organoaluminum oxy-compound [B], the compound [C] and the organoaluminum compound [D] can be contacted with each other at a temperature of usually xe2x88x92100 to 200xc2x0 C., preferably xe2x88x9270 to 100xc2x0 C.
In the present invention, copolymerization of ethylene and the xcex1-olefin of 3 to 20 carbon atoms can be carried out under the conditions of a temperature of usually 40 to 200xc2x0 C., preferably 50 to 150xc2x0 C., particularly preferably 60 to 120xc2x0 C., and a pressure of atmospheric pressure to 100 kg/cm2, preferably atmospheric pressure to 50 kg/cm2, particularly preferably atmospheric pressure to 30 kg/cm2.
This polymerization reaction can be conducted by various polymerization processes, but it is preferably conducted by a solution polymerization process. In the solution polymerization process, the aforesaid hydrocarbon solvents are employable as the polymerization solvents.
Though the copolymerization can be carried out by any of batchwise, semi-continuous and continuous processes, it is preferably carried out continuously. The polymerization can be carried out in two or more stages under different reaction conditions.
The long-chain branched ethylene/xcex1-olefin random copolymer used in the invention are obtained by the processes mentioned above, and the molecular weight of the copolymer can be modified by varying the polymerization conditions such as polymerization temperature or controlling the amount of hydrogen (molecular weight modifier).
To the soft resin composition according to the present invention, additives such as antioxidant, UV-light absorber, light resisting agent, phosphite heat stabilizer, peroxide decomposer, basic co-stabilizer, nucleating agent, plasticizer, lubricant, antistatic agent, flame retardant, pigment, dye and filler can be optionally added as far as it is not prejudicial to the object of the invention.
Examples of the filler include carbon black, asbestos, talc, silica and silica-alumina.
To the soft resin composition of the present invention, the other polymer may be blended as far as it is not prejudicial to the object of the invention.
Examples of the other polymer include EPT, polypropylene, various engineering plastics (polyamide, polyester and etc.).
The (soft) resin composition according to the present invention can be prepared by melt-kneading the ethylene/xcex1-olefin random copolymer (B), the polyethylene resin (A), and optionally blended additives as described below by the various conventional method.
(1) Namely, the (soft) resin composition of the present invention can be prepared by simultaneously or successively introducing each of the components (polyethylene resin (A), ethylene/xcex1-olefin copolymer resin (B) and optionally added additives) into Henschel mixer, a twin-cylinder mixer, a tumbling mixer, a ribbon blender or the like to mix them and then melt-kneading the resultant mixture by a kneading machine such as a single-screw extruder, a multi-screw extruder, a kneader and Banbury mixer.
By using the kneading machine excellent in kneading performance such as the kneader and Banbury mixer, high quality (soft) resin compositions containing polyethylene resin, in which each of components are further homogenously dispersed, can be produced.
The additives such as antioxidant can be optionally added in an optional stage of the preparation process.
The (soft) resin composition of the invention thus prepared can be molded into moldings having various shapes by the conventional various melt molding method including injection molding, extrusion molding and compression molding.
(2) In the present invention, the (soft) resin composition can be prepared by a process comprising dissolving the polyethylene resin (A), the long-chain branched ethylene/xcex1-olefin random copolymer (B) and optional additives as described above in a suitable solvent (e.g., hydrocarbon solvents such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene) and then removing the solvent.
(3) The (soft) resin composition can be prepared by dissolving the polyethylene resin (A), the long-chain branched ethylene/xcex1-olefin random copolymer (B) and optional additives as described above in suitable solvents, respectively, to prepare solutions separately followed by mixing the solutions, and removing the solvents.
(4) The process in which any of the processes (1) to (3) are combined is also employable.
Hereinafter, the ethylene/xcex1-olefin copolymer resin composition and the use thereof are concretely described.
The ethylene/xcex1-olefin copolymer resin composition according to the present invention comprises a linear ethylene/xcex1-olefin copolymer (A-0) out of the polyethylene resin (A) and a long-chain branched ethylene/xcex1-olefin random copolymer (B-xcex1).
Hereinafter, compositions of each components, physical properties, preparation processes of the polyethylene resin (A-xcex1) and the ethylene/xcex1-olefin random copolymer resin (B-xcex1) suitably used for the ethylene/xcex1-olefin copolymer resin composition are described. These properties of the polyethylene resin (A-xcex1) and the copolymer resin (B-xcex1) are the same as those of the polyolefin resin (A) and the ethylene/xcex1-olefin random copolymer resin (B), respectively, except for those described below, otherwise specifically mentioned.
The linear ethylene/xcex1-olefin copolymer resin (A-0) used in the invention comprises ethylene and an xcex1-olefin of 4 to 20 carbon atoms, as described above.
The linear ethylene/xcex1-olefin copolymer (A-0) has a density of 0.901 to 0.940 g/cm3, preferably 0.905 to 0.930 g/cm3, more preferably 0.905 to 0.925 g/cm3. The linear ethylene/xcex1-olefin copolymer having a density of less than 0.901 g/cm3 is not suitable because, in case of using it, a film made from the resultant composition has low rigidity and is likely to cause blocking, and, further, heat seal strength thereof is apt to decrease, though having excellent in impact resistance and low temperature heat-sealing properties. While, the linear ethylene/xcex1-olefin copolymer having a density of more than 0.940 g/cm3 is not suitable because, in case of using it, impact strength and low temperature heat-sealing properties of the resultant film are apt to be decreased.
The linear ethylene/xcex1-olefin copolymer (A-0) has a melt flow rate (MFR, ASTM D 1238, 190xc2x0 C., a load of 2.16 kg) of 0.01 to 20 g/10 min, preferably 0.05 to 10 g/10 min, more preferably 0.1 to 7 g/10 min. The linear ethylene/xcex1-olefin copolymer having a melt flow rate of less than 0.01 g/10 min is not suitable because, in case of using it, the resultant composition requires too high processing torque to process it by an ordinary process. While, the linear ethylene/xcex1-olefin copolymer having a density of more than 20 g/10 min is not suitable because, in case of using it, the stability of the bubble become worse so that inflation molding thereof can not be performed.
The liner ethylene/xcex1-olefin copolymer (A-0) having the above properties can be prepared by the process as described above, which comprises copolymerizing ethylene and xcex1-olefin having 4 to 20 carbon atoms in the presence of a transition metal catalyst.
The long-chain branched ethylene/xcex1-olefin random copolymer (B-xcex1) used in the invention comprises ethylene and an xcex1-olefin of 3 to 20 carbon atoms, as described above.
The ethylene/xcex1-olefin random copolymer (B-xcex1) has a density of 0.860 to 0.900 g/cm3, preferably 0.865 to 0.900 g/cm3 more preferably 0.870 to 0.895 g/cm3. When the long-chain branched ethylene/xcex1-olefin random copolymer having a density of more than 0.900 g/cm3 is used, a film made from the resultant composition is likely to have poor low temperature heat-sealing properties and tear strength thereof is apt to decrease. While, when the long-chain branched ethylene/xcex1-olefin random copolymer having a density of less than 0.860 g/cm3 is used, the resultant composition is difficult to handle as the pellets thereof and the film made from the composition is apt to get worse in anti-blocking and slipping properties.
The long-chain branched ethylene/xcex1-olefin random copolymer (B-xcex1) has a melt flow rate (MFR, ASTM D 1238, 190xc2x0 C., a load of 2.16 kg) of 0.01 to 20 g/10 min, preferably 0.1 to 10 g/10 min, more preferably 0.5 to 5 g/10 min.
An intrinsic viscosity (xcex7), glass transition temperature (Tg), molecular weight distribution (Mw/Mn) obtained by GPC, B value, gxcex7* value, preparation process (including the catalyst) and so on of the long-chain branched ethylene/xcex1-olefin random copolymer resin (B-xcex1) are the same as described above.
The ethylene/xcex1-olefin random copolymer has characteristics such that the molecular weight distribution and composition distribution thereof are narrow and the melt tension thereof is high since it has a long chain branching.
The ethylene/xcex1-olefin copolymer resin composition of the invention contains 60 to 95% by weight, preferably 60 to 90% by weight of the polyethylene (A-0) and 5 to 40% by weight, preferably 10 to 40% by weight of the long-chain branched ethylene/xcex1-olefin random copolymer (B-xcex1), based on 100% by weight of the total amount of the liner ethylene/xcex1-olefin copolymer (A-0) and the long-chain branched ethylene/xcex1-olefin random copolymer (B-xcex1).
In other words, the ethylene/xcex1-olefin copolymer resin composition contains the long-chain branched ethylene/xcex1-olefin random copolymer (B-xcex1) of 5 to 67 parts by weight, preferably 11 to 67 parts by weight, based on 100 parts by weight of the polyethylene resin (A-0) of the polyethylene resin (A).
The ethylene/xcex1-olefin copolymer resin composition having such formulation as described above is especially suitable for using as films, excellent in heat stability and suitability in high-speed molding, and can provide films excellent in mechanical strength properties, low temperature heat-sealing properties and sealing stability, and further slip characteristics and anti-blocking properties thereby being excellent in handling properties and suitability for high-speed filling upon packaging by automatic filling machines.
To the ethylene/xcex1-olefin copolymer resin composition of the invention, various additives such as weathering stabilizer may be optionally blended as far as it is not prejudicial to the object of the invention.
The ethylene/xcex1-olefin copolymer resin composition of the invention can be prepared by the conventional method as described above
The film according to the present invention is formed from the ethylene/xcex1-olefin copolymer resin composition of the invention.
The film of the invention has a thickness of 10 to 200 xcexcm.
The film of the invention can be obtained by molding the ethylene/xcex1-olefin copolymer resin composition of the invention by the conventional process such as air-cooled inflation molding, two-level air-cooled inflation molding, high-speed inflation molding, T-die film formation or water-cooled inflation molding.
The film made by the above-described method has an excellent balance between transparency and rigidity, keeping heat-sealing properties, hot tack and heat resistance which the conventional LLDPEs also have. Further, since the long-chain branched ethylene/xcex1-olefin random copolymer (B-xcex1) constituting the above composition has particularly low composition distribution, the surface of the film is not sticky.
The resin composition of the present invention is excellent in moldability and capable of providing moldings having excellent pliability.
Particularly, the soft resin composition of the present invention is excellent in melt flow characteristics, namely excellent in moldability, and is capable of providing moldings excellent in balance between pliability and heat resistance.
Especially, the ethylene/xcex1-olefin copolymer resin composition of the invention is excellent in heat stability and suitability for high-speed molding, and can provide the films excellent in mechanical strength properties, low temperature heat-sealing properties and sealing stability, and further in slip characteristics and anti-blocking properties, thereby being excellent in handling porperties and suitability for high-speed filling upon packaging by automatic filling machiens.
The film of the present invention comprises the above ethylene/a-olefin copolymer resin composition to be mechanical strength properties, low temperature heat-sealing properties and sealing stability, and further in slip characteristics and anti-blocking properties thereby being excellent in handling properties and suitability for high-speed filing upon packaging by automatic filling machines.
Accordingly, the films of the invention can be suitably used for standard sacks, heavy duty sacks, wrapping films, raw-film for lamination, sugar sacks, oil bags, water bags, various packaging film such as packaging films for foods, infusion bags and agricultural materials. The films of the invention can be used for multi-layered films by laminating with a base material of nylon, polyester or the like. Of these, the film of the invention is particularly suitable for the wrapping films.
In addition, the ethylene/xcex1-olefin copolymer resin composition of the invention is also employable for blow-molded infusion bags and bottles, extrusion molded tubes, pipes and pull-off caps, injection molded articles such as daily necessaries, fibers and big size moldings made by rotomolding.